The present invention relates to novel silicones for powder treatment, powders having the surface treated with such silicones, and cosmetic materials containing such surface-treated powders. More specifically, the invention is concerned with silicones that are used for surface treatment of powders to provide the treated powders with high affinity for general fats and oils, such as ester oils and glycerides, silicone oils and fluorinated oils, and further with cosmetic materials which contain the powders having the surface treated with the aforesaid silicones to acquire excellent dispersibility and stable emulsion state and ensure a dry feel for the users.
In general the makeup is smeared with secretion from humans, such as sweat, tear and sebum. In particular, the leading cause of the makeup spoilage consists in that the powder in a cosmetic material is wetted excessively by the sebum secreted from the skin in addition to oil ingredients compounded in the cosmetic material. Therefore, with the intention of reducing the oil ingredients remaining on the skin after the makeup is done, it has been attempted to use volatile oils, such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, as a part of the oil ingredients compounded in a cosmetic material.
Further, the rub and the water given to the makeup constitute external factors inhibiting the makeup effect from lasting long. For the purpose of preventing the makeup from coming off by contact with aqueous substances, such as sweat and tears, or maintaining the skin protecting effect by preventing a loss of water-soluble components and sebum in the skin, it has been carried out to heighten the water repellency by mixing a silicone oil in the cosmetic material. In recent years, the silicone oils, represented, e.g., by dimethylpolysiloxanes, have been prevailingly used as an oil ingredient for cosmetic materials because of their characteristics, including light feel, excellent water repellency and high safety.
On the other hand, the pigments represented by ferric oxide red and titanium dioxide, and powders such as mica and sericite are widely used in the field of cosmetics, including nail color, nail coat, face powder, mascara and eye liner. In using these powders for cosmetics, the powder surface is generally subjected to treatment with metal soap, alumina, silica or phosphoric acid for the purpose of imparting sufficient water repellency and safety to the powders.
For instance, the method ofusing 12 to 60 parts by weight of methylhydrogenpolysiloxanes per 100 parts by weight of powders to effect surface treatment of the powders is disclosed in Japanese Patent 2,719,303, and the method of using the straight-chain silicone having one alkoxy-modified end for surface treatment of powders is disclosed in Japanese Tokkai Hei 7-196946 (the term xe2x80x9cTokkaixe2x80x9d as used herein means an xe2x80x9cunexamined published patent applicationxe2x80x9d). Although the powder treatment with silicones is a generally known art, it has been desired to develop special silicones capable of ensuring further improvements in compatibility between the treated powders and general oils, fluorinated oils or silicone oils, and besides, enhanced stability in emulsions containing both treated powders and those oils.
As a result of our intensive studies aiming at developing cosmetic materials having a light feel, sufficiently high water repellency and a makeup effect of long-duration, it has been found that the powders treated with one-end reactive silicone-grafted silicone compounds have extremely high water repellency, sufficient dispersibility in volatile oils, such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, and good usability as powders for cosmetic materials, and besides, the cosmetic materials using them have a light feel, thereby achieving the present invention.
Therefore, a first object of the invention is to provide a powder-treating agent which has good affinity for fats and oils used in general cosmetic materials and can impart excellent capability for emulsification to the powder.
A second object of the invention is to provide a powder having good affinity for fats and oils used in general cosmetic materials and high capability for emulsification.
A third object of the invention is to provide a cosmetic material having excellent storage stability in an emulsified condition.
The above-described objects are attained with silicones represented by the following formula (1) as a powder-treating agent, a powder treated with the aforesaid silicones, and a cosmetic material containing the aforesaid powder:
R1aR2bR3cSiO(4xe2x88x92axe2x88x92bxe2x88x92c)/2xe2x80x83xe2x80x83(1)
wherein R1 groups, which are the same or different, each represent an organic group selected from the class consisting of alkyl groups containing 1 to 30 carbon atoms, aryl groups, aralkyl groups, fluorinated alkyl groups and organic groups represented by the following formula (2); R2 groups each represent a reactive substituent selected from the class consisting of a hydrogen atom, a hydroxyl group and alkoxy groups containing 1 to 6 carbon atoms, which is attached to a silicon atom in the siloxane chain directly or via a linkage group comprising at least one carbon, oxygen or silicon atom; R3 groups each represent a silicone compound residue represented by the following formula (3); a is a number of from 1.0 to 2.5; b is a number of from 0.001 to 1.5; and c is a number of from 0.001 to 1.5 
wherein R4 is a hydrocarbon group containing 4 to 30 carbon atoms or an organic group represented by R5xe2x80x94(CO)xe2x80x94; R5 is a hydrocarbon group containing 1 to 30 carbon atoms; d is an integer of from 0 to 15, e is an integer of from 0 to 50, and f is an integer of from 0 to 50; and x is an integer of from 1 to 5, and y is an integer of from 0 to 500.
The powders surface-treated with the aforementioned silicones have good affinity for oils generally used in cosmetic materials, such as other silicone oils, ester oils and hydrocarbon oils, and so they have excellent capability for emulsification. Therefore, the emulsions using the powders surface-treated with the present silicones have excellent storage stability, and so they can be effectively applied to cosmetic materials.
As described above, the present silicone compounds are represented by formula R1aR2bR3cSiO(4xe2x88x92axe2x88x92bxe2x88x92c)/2 (referred to as formula (1)).
Each R1 group in formula (1) represents an organic group selected from the class consisting of 1-30C alkyl groups, aryl groups, aralkyl groups, fluorinated alkyl groups and organic groups represented by xe2x80x94CdH2dxe2x80x94Oxe2x80x94(C2H4O)e(C3H6O)fR4 (which is referred to as formula (2)), wherein d, e and f are each an integer and fall within the following ranges: 0xe2x89xa6dxe2x89xa615, 0xe2x89xa6exe2x89xa650, 0xe2x89xa6fxe2x89xa650; R4 represents a 4-30C hydrocarbon group or an acyl group represented by R5xe2x80x94(CO)xe2x80x94; and R5 represents a 1-30C hydrocarbon group.
Examples of an alkyl group as R1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group; those of a cycloalkyl group as R1 include a cyclopentyl group and a cyclohexyl group; those of an aryl group as R1 include a phenyl group and a tolyl group; those of an aralkyl group as R1 include a benzyl group and a phenetyl group; and those of a fluorinated alkyl group as R1 include a trifluoropropyl group and a heptadecafluorodecyl group.
In addition, examples of an organic group represented by formula (2) include higher alcohol residues, such as residues of higher alcohols, such as cetyl alcohol, oleyl alcohol and stearyl alcohol, and polyoxyalkylene adducts thereof; higher alcohol alkenyl ether residues, and polyoxyalkylene adducts thereof; higher fatty acid residues, such as residues of oleic acid, stearic acid and behenic acid, and polyoxyalkylene adducts thereof; and higher fatty acid alkenyl ester residues and polyoxyalkylene adducts thereof.
More specifically, the formula (2) is xe2x80x94Oxe2x80x94(C2H4O)e(C3H6O)fR3 when d is 0. Further, it becomes xe2x80x94Oxe2x80x94R3 in the case of e=0 and f=0, and represents a residue of higher alcohol such as cetyl alcohol, oleyl alcohol or stearyl alcohol, or a residue of higher fatty acid such as oleic acid, stearic acid or behenic acid. In a case of e,fxe2x89xa71, on the other hand, the formula (2) represents an alcohol residue of higher alcohol/alkylene oxide adduct (having OH at the end).
When d is 1 or 2 the formula (2) is xe2x80x94CdH2dxe2x80x94Oxe2x80x94(C2H4O)e(C3H6O)fR3 and this group is formed by dehydrohalogenation reaction between Sixe2x80x94OH group and X(CH2)nxe2x80x94Oxe2x80x94(C2H4O)e(C3H6O)fR3 (wherein X is halogen).
The xe2x80x94CdH2dxe2x80x94Oxe2x80x94(C2H4O)e(C3H6O)fR3 group in the case of dxe2x89xa73 is a group introduced by the addition reaction between Sixe2x80x94H and a higher alcohol alkenyl ether or a fatty acid alkenyl ester, or a polyalkylene oxide adduct thereof.
R2 groups are each a reactive substituent selected from the class consisting of a hydrogen atom, a hydroxyl group and alkoxy groups containing 1 to 6 carbon atoms such as methoxy, ethoxy and isopropoxy groups. And this reactive substituent is attached to a silicon atom in the siloxane chain directly or via a linkage group comprising at least carbon, oxygen or silicon atom, such as an alkylene group or an alkylene ether linkage. For instance, such reactive substituents can be introduced into the present compounds by addition reaction between SiH groups and vinyltrichlorosilane, vinyltris (xcex2-methoxyethoxy)silane, vinyltrimethoxysilane or vinyltriethoxysilane.
In the case of using silicone compounds for cosmetics, the evolution of methanol and hydrogen gas caused by methoxy groups and SiH groups remaining unreacted becomes a problem. Therefore, the desirable reactive substituent is a hydroxyl or ethoxy group. Such a reactive substituent may be a monofunctional, difunctional or trifunctional group, with examples including dimethylethoxysilyl, diethoxymethylsilyl and triethoxysilyl groups.
R3 groups are each a silicone compound residue represented by the following formula (3): 
wherein x is an integer of from 1 to 5, and y is an integer of from 0 to 500, preferably from 3 to 100. For instance, x has a value of 2 when the silicone compound residue of formula (3) is introduced by the reaction between a vinyl group and hydrogensiloxane. When the integer xe2x80x9cyxe2x80x9d in R3 has a value greater than 500, the resultant R3 group tends to cause a problem of lowering the reactivity in the introduction into the hydrogensiloxane constituting the main chain.
xe2x80x9caxe2x80x9d in formula (1) is a number of from 1.0 to 2.5, preferably from 1.2 to 2.3, and xe2x80x9cbxe2x80x9d in formula (1) is a number of from 0.001 to 1.5, preferably from 0.05 to 1.0. When b is smaller than 0.001, the reactivity of such a silicone with powders is low. xe2x80x9ccxe2x80x9d in formula (1) is a number of from 0.001 to 1.5, preferably from 0.05 to 1.0. When these requirements are fulfilled, the compatibility of the present silicones with general silicone oils can be fully achieved.
When the present silicone compounds represented by formula (1) are used as a powder surface-treating agent, the weight average molecular weight suitable therefor, though it has no particular limits, is from 300 to 100,000. When the silicone compound of formula (1) has a weight average molecular weight higher than 100,000, it has a sticky feel because of its high viscosity; while, when the silicone compound has a weight average molecular weight lower than 300, it cannot provide smooth texture which is a characteristic of silicones. In particular, it is desirable for the present silicone compounds to have their weight average molecular weight in the range of 1,000 to 10,000.
The present silicone compounds represented by formula (1) can be synthesized with ease by addition reaction between organohydrogenpolysiloxanes and silicone compounds represented by the following general formula (4) and, if desired, alkene compounds as well in the presence of a platinum or rhodium catalyst: 
wherein R1, x and y have the same meanings as in formula (3) respectively.
The organohydrogenpolysiloxanes used therein may have a straight-chain structure or a cyclic structure. However, the straight-chain organohydrogenpolysiloxanes are preferable because they have better addition reactivity. Additionally, the organohydrogen polysiloxanes have no particular restriction as to the bonding site of SiH group(s), but the SiH group(s) may be situated in side chain(s) or at the molecular end(s).
The mixing ratio of the organohydrogenpolysiloxanes to the combination of the silicone compound of formula (4) and the alkene compound can be from 0.2 to 2.0, expressed in terms of the quantity by mole of the terminal unsaturated group per mole of SiH groups. Preferably, the foregoing ratio is adjusted to the range of 0.5 to 1.2 in order to avoid the evolution of hydrogen gas caused by the SiH groups remaining unreacted.
The foregoing addition reaction is carried out effectively in the presence of a platinum catalyst or a rhodium catalyst. Suitable examples of such a catalyst include chloroplatinic acid, alcohol-modified platinic chloride and platinic chloride-vinylsiloxane complex.
The amount of catalyst used, though it may be a conventional catalytic amount, is desirably at most 500 ppm, particularly desirably at most 20 ppm, based on the platimum or the rhodium. The addition reaction may be carried out in an organic solvent, if needed. Examples of an organic solvent usable therein include aliphatic alcohols, such as methanol, ethanol, 2-propanol and butanol; aromatic hydrocarbons, such as toluene and xylene; aliphatic or alicyclic hydrocarbons, such as n-pentane, n-hexane and cyclohexane; and halogenated hydrocarbons, such as dichloromethane, chloroform and carbon tetrachloride.
The addition reaction has no particular restriction as to its reaction conditions. However, it is desirable that the addition reaction be-performed for 1 to 10 hours under reflux.
The present silicone compounds can be used for various purposes. In particular, they are suitable for treatment of powder surface. In this case, the appropriate proportion of the silicone compound represented by formula (1) mixed with a powder is from 0.1 to 30 parts by weight, preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the powder.
The present silicone compounds are applicable to surface treatment of any powders so far as the powders can be used in general cosmetic materials, irrespective of their shape (whether it is spherical, acicular or tabular), their size (whether it is on the order of fume, fine grain or pigment), and their structure (whether it is porous or nonporous) Examples of powders usable in the invention include inorganic powders (including white pigments and extender pigments), organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metallic powder pigments and natural colors. Of these powders, white pigments, such as zinc oxide and titanium dioxide, and extender pigments, such as mica and sericite, are especially suitable for the treatment with the present silicones.
The present silicone compounds as powder-treating agents can achieve the powder-surface treatment in accordance with any of known methods. For instance, the method applied to the present treatment can be selected properly from the following methods:
1. A method of dispersing the desired powder into a treating agent-mixed water or organic solvent to treat the powder surface.
2. A method of mixing a powder with a powder-treating agent and then grinding the resulting mixture with a grinder, such as a ball mill or a jet mill, to treat the powder surface.
3. A method of mixing a silicone oil (especially methylhydrogenpolysiloxanes or methylhydroxypolysiloxanes) with a solvent, dispersing a powder into the resultant mixture to adsorb the silicone oil to the powder surface and then drying the resulting powder so as to cause sintering.
The powder whose surface is treated with the present silicone compound can be mixed in a cosmetic material in a proportion of from about 0.1 to about 99 weight %, although the suitable proportion depends on the type and the state of the cosmetic material.
The cosmetic materials in which the powders treated with the present silicone compounds are incorporated (which are referred to as xe2x80x9cthe present cosmetic materialsxe2x80x9d) can further contain oils depending on the desired purposes thereof. In the present cosmetic materials, any unctuous agents can be used whether they are ina solid, semisolid or liquid state, provided that they have so far been used for general cosmetics.
More specifically, not only natural animal and vegetable fats and oils but also semi-synthetic fats and oils can be mixed in the present cosmetic materials, with examples including avocado oil, linseed oil, almond oil, Chinese wax, perilla oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candellila wax, beef tallow, beef foot oil, beef bone fat, hydrogenated beef tallow, apricot kernel oil, spermaceti, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice branoil, sugarcanewax, sasanquaoil, saffloweroil, shea butter, Chinese tung oil, cinnamon oil, jojoba wax, shellac wax, turtle oil, soybean oil, tea seed oil, tsubaki oil, evening primrose oil, corn oil, lard, rape seed oil, Japanese tung oil, rice-bran wax, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil, caster oil fatty acid methyl ester, sunflower oil, grape seed oil, bayberry wax, jojoba oil, macadamia nut oil, beeds wax, mink oil, cottonseed oil, cotton wax, Japan wax, haze kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride, mutton-tallow, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and egg yolk oil. Additionally, the term xe2x80x9cPOExe2x80x9d as used herein stands for polyoxyethylene.
Examples of hydrocarbon oil which can be mixed therein include ozokerite, squalane, squalene, ceresine, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax and Vaseline; and those of a higher fatty acid which can be mixed include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid and 12-hydroxystearic acid.
Examples of a higher alcohol which can be mixed therein include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol) and monooleyl glyceryl ether (cerakyl alcohol).
Examples of ester oil which can be mixed therein include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkylglycol monoisostearates, isocetyl isostearate, trimethylolpropane triisostearic acid ester, ethylene glycol di-2-ethylhexanoic acid ester, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoic acid ester, pentaerythritol tetra-2-ethylhexanoic acid ester, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicapric acid ester, triethyl citrate, 2-ethylhexyl cinnamate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acid esters, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethylocanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutaminic acid 2-octyldodecyl ester and diisostearyl malic acid; and examples of glyceride oil which can be mixed therein include acetoglyceride, triisooctanoic acid glycride, triisostearic acid glyceride, triisopalmitic acid glyceride, tri-2-ethylhexanoic acid glyceride, monostearic acid glyceride, di-2-heptylundecanoic acid glyceride, trimyristic acid glyceride and myristic acid isostearic acid diglyceride.
As examples of a silicone oil which can be mixed, mention may be made of organopolysiloxanes having from low to high viscosities, such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane and a copolymer of dimethylsiloxane and methylphenylsiloxane; cyclic siloxanes, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyl-tetrahydrogencyclotetrasiloxane; silicone rubbers, such as gummy dimethylpolysiloxanes having high polymerization degrees and gummy dimethylsiloxane-methylphenylsiloxane copolymers having high polymerization degrees; and cyclosiloxane solutions of silicone rubber, trimethylsiloxysilicate, cyclosiloxane solutions of trimethylsiloxysilicate, higher alkoxy-modified silicones such as stearoxysilicone, higher fatty acid-modified silicones, alkyl-modified silicones, amino-modified silicones, fluorine-modified silicones, and solutions of silicone resin.
As examples of fluorine-containing oil which can be mixed, mention may be made of perfluoropolyether, perfluorodecalin and perfluorooctane.
Furthermore, the present cosmetic materials can contain one or more of a surfactant, if desired. The surfactant contained therein has no particular restriction, but it may be any of anionic, cationic, nonionic and amphoteric ones so long as they have hitherto been used in general cosmetics. In particular, the surfactants having their HLB values in the range of 2 to 8 are suitable for the present cosmetic materials.
Examples of a usable anionic surfactant include fatty acid soap, such as sodium stearate or triethanolamine palmitate; alkyl ether carboxylic acids and salts thereof; salts of amino acid-fatty acid condensates; alkanesulfonates; alkenesulfonates; sulfonated fatty acid esters; sulfonated fatty acid amides; sulfonates of formaldehyde condensate type; alkylsulfates; higher secondary alcohol sulfates; alkyl and aryl ether sulfates; fatty acid ether sulfates, fatty acid alkylolamide sulfates; ether sulfates, such as Turkeky red oil; alkyl phosphates; ether phosphates; alkyl aryl ether phosphates; amide phosphates; and active agents of N-acylamino acid type.
Examples of a usable cationic surfactant include amine salts, such as alkylamie salts, polyamines and aminoalcohol fatty acid derivatives, quaternary alkylammonium salts, quaternary arylammonium salts, pyridinium salts and imidazolium salts.
Examples of a usable nonionic surfactant include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ehter, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxanes, organopolysiloxanes modified with both polyoxyalkylene and alkyl groups, alkanolamides, sugar ethers and sugar amides; and examples of a usable amphoteric surfactant include betaine, aminocarboxylates and imdazoline derivatives.
In the present cosmetic materials, another powder can further be used depending on the desired purposes. Such a powder is not particularly restricted as to its shape (whether it is spherical, acicular or tabular), its size (whether it is on the order of fume, fine grain or pigment), and its structure (whether it is porous or nonporous), provided that it has so farbeenusedin conventional cosmetic materials. For instance, inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metallic powder pigments and natural colors can be used in the present cosmetic materials, if desired.
Examples of a usable inorganic powder include titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, ruby mica, biotite, lipidolite, silicic acid, silicic acid anhydride, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal salts of tungstic acid, hydroxyapatite, vermiculite, haidilite, bentonite, montmorillonite, hectorite, zeolite, ceramics powder, calcium secondary phosphate, alumina, aluminum hydroxie, boron nitride and silica.
Examples of a usable organic powder include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethylmethacrylate powder, cellulose powder, silk powder, nylon powder such as 12-nylon powder or 6-nylon powder, silicone powder, styrene-acrylic acid copolymer powder, divinylbenzene-styrene copolymer powder, vinyl resin powder, urea resin powder, phenol resin powder, fluororesin powder, silicone resin powder, acrylic resin powder, melamine resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder, starch powder and lauroyl lysine powder.
Examples of a usable surfactant metal salt powder (metal soap powder) include powders of zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magensium myristate, zinc cetylphosphate, calcium cetylphosphate and zinc sodium cetylphosphate.
Examples of a usable colored pigment include inorganic red pigments, such as iron oxide, iron hydroxide and iron titanate; inorganic brown pigments, such as xcex3iron oxide; inorganic yellow pigments, such as iron oxide yellow and loess; inorganic black pigments, such as iron oxide black and carbon black; inorganic violet pigments, such as manganese violet and cobalt violet; inorganic green pigments, such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate; inorganic blue pigments, such as Prussian blue and ultramarine blue; lakes of tar pigments; lakes of natural dyes; and synthetic resin powder complexes of the inorganic pigments as recited above.
Examples of a usable pearl pigment include titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scales, and titanium oxide-coated colored mica; and examples of a usable metallic powder pigment include aluminum powder, copper powder and stainless powder.
Examples of a usable tar pigment include Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206 and Orange No. 207 (according to the pigment nomenclature method in JIS); and examples of a usable natural pigment include powders of carminic acid, laccaic acid, carthamin, bradilin and crocin.
Additionally, complexes of the powders as recited above or those obtained by treating the powders as recited above with general oil, a silicone oil other than the present silicone compounds, a fluorine-containing compound or a surfactant may be used. Also, these powders may be used as a mixture of two or more thereof, if desired.
In the present cosmetic materials, the compounds having at least one alcoholic hydroxyl group per molecule can be used depending on the desired purposes of the cosmetic materials.
Examples of alcohols which can be added include lower alcohols, such as ethanol and isopropanol; sugar alcohols, such as sorbitol and maltose; and sterols, such as cholesterol, sitosterol, phytosterol and lanosterol.
Examples of water-soluble polymers which can be added include vegetable polymers, such as gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch (rice, corn, potato, wheat), alge colloid, tranto gum and locust bean gum; microbial polymers, such as xanthan gum, dextran, succinoglucan and pullulan; animal polymers, such as collagen, casein, albumin and gelatin; starch polymers, such as carboxymethyl starch and methylhydroxypropyl starch; cellulose polymers, such as methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose and powdery cellulose; alginic acid polymers, such as sodium alginate and propylene glycol ester of alginic acid; vinyl polymers, such as polyvinyl methyl ether and carboxyvinyl polymer; polyoxyethylene polymers; polyoxyethylene-polyoxypropylene copolymers; acrylic polymers, such as sodium polyacrylate, polyethylacrylate and polyacrylamide; other synthetic water-soluble polymers, such as polyethyleneimines and cationic polymers; and inorganic water-soluble polymers, such as bentonite, aluminum magnesium silicate, montmorillonite, beidellite, nontronite, saponite, hectorite and silicic acid anhydride.
In these water-soluble polymers, film-forming agents, such as polyvinyl alcohol and polyvinyl pyrrolidine, are also included.
The present cosmetic materials can further contain one or more kinds of cross-linked organopolysiloxanes depending on their respectively desired purposes.
The cross-linked organopolysiloxanes suitable for the present cosmetic materials are those which cause swelling when they contain a silicone having low viscosity of from 0.65 to 10.0 mm2/sec (25xc2x0) in a quantity larger than their self weight. Further, it is desirable that the cross-linked structure of those organopolysiloxanes be formed by the reaction between the hydrogen atoms bonded directly to silicon atoms and a cross-linking agent having at least two vinylic reactive moieties per molecule. Furthermore, it is desirable in the foregoing reaction to use the cross-linking agent containing at least one moiety selected from polyoxyalkylene, alkyl, alkenyl, aryl and fluoroalkyl moieties. The suitable proportion of such cross-linked organopolysiloxanes mixed in a cosmetic material according to the invention is from 0.1 to 30 weight %, preferably from 1.0 to 10 weight %, to the total weight of the cosmetic material.
The present cosmetic materials can further contain one or more kinds of silicone resins, such as acryl-silicone graft or block copolymers and silicone compounds having network structure, if needed.
In particular, acrylsilicone resins are suitable for the present cosmetic materials. Further, it is desirable that at least one moiety selected from the group consisting of pyrrolidone, long-chain alkyl, polyoxyalkylene and fluoroalkyl moieties be present in such an acrylsilicone resin molecule. The other favorable silicone resins are silicone compounds having network structure. When the silicone resins, such as acryl-silicone graft or block copolymer and silicone compounds having network structure, are mixed in the present cosmetic material, the appropriate proportion of silicone resins mixed is from 0.1 to 20 weight %, preferably from 1 to 10 weight %, to the total weight of the cosmetic material.
To the present cosmetic materials, the ingredients used in general cosmetic materials, such as oil-soluble gelling agents, clay minerals modified with organic compounds, resins, ultraviolet absorbents, moisture-holding agents, antiseptics,. antimicrobial agents, perfume, salts, antioxidants, pH regulators, chelating agents, refrigerant, anti-inflammatory agents, skin beautifying components (a skin whitener, a cell activator, a rough dry skin improver, a blood circulation promoter, a skin astringent and an anti-seborrheic agent), vitamins, amino acids, nucleic acids, hormones and clathrate compounds, can be added so far as they have no adverse influence on the effects of the present invention.
Examples of an oil-soluble gelling agent which can be added include metal soaps, such as aluminum stearate, magnesium stearate and zinc myristate; amino acid derivatives, such as N-lauroyl-L-glutamic acid and xcex1,xcex3-di-n-butylamine; dextrin fattyacidesters, such as dextrinpalmitic acid ester, dextrin stearic acid ester and dextrin 2-ethylhexaminic acid palmitic acid ester; sucrose fatty acid esters, such as sucrose palmitic acid ester and sucrose stearic acid ester; benzylidene derivatives of sorbitol, such as monobenzylidene sorbitol and dibenzylidene sorbitol; and clay minerals modified with organic compounds, such as dimethylbenzyldodecyl ammonium montmorillonite clay and dimethyldioctadecyl ammonium montmorillonite clay.
Examples of an ultraviolet absorbent which can be added include ultraviolet absorbents of benzoic acid type, such as p-aminobenzoic acid; those of anthranilic acid type, such as methyl anthranilate; those of salicylic acid type, such as methyl salicylate; those of succinic acid type, such as octyl p-methoxysuccinate; those of benzophenone type, such as 2,4-dihydroxybenzophenone; those of urocanic acid type, such as ethyl urocanate; and those of dibenzoylmethane type, such as 4-t-butyl-4xe2x80x2-methoxydibenzoylmethane.
Examples of a moisture-holding agent which can be added include glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluromic acid, chondroitin sulfuric acid, pyrrolidone carboxylic acid, polyoxyethylene glycoside, and polyoxypropylene methylglycoside.
Examples of an antiseptic agent which can be added include alkyl p-hydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate and phenoxyethanol; and those of an antimicrobial agent which can be added include benzoic acid, salicylic acid, carbolic acid, sorbic acid, alkyl p-hydroxybenzoates, p-chlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer and phenoxyethanol.
Examples of an antioxidant which can be added include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene and phytic acid; those of a pH regulator which can be added include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate and ammonium hydrogen carbonate; those of a chelating agent which can be added include alanine, sodium ethylenediaminetetraacetate, sodium polyphosphate, sodium metaphosphate and phosphoric acid; those of a refrigerant which can be added include L-menthol and camphor; and those of an anti-inflammatory agent which can added include allantoin, glycyrrhizin and salts thereof, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid and azulene.
Examples of a skin-beautifying component which can be added include whitening agents, such as placenta extract, arbutin, glutathione and Yukinoshita extract; cell activators, such as royal jelly, photosensitizer, cholesterol derivatives and calf blood extract; rough dry skin improvers; blood circulation improvers, such as nonylic acid vanillyl amide, benzyl nicotinate, xcex2-butoxyethyl nicotinate, capsaicin, zingerone, cantharis tincture, ichtammol, caffeine, tannic acid, xcex1-borneol, tocopheryl nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetyl choline, verapamil, cepharanthin and xcex3-oryzanol; skin astringents, such as zinc oxide and tannic acid; and anti-seborrheic agents, such as sulfur and thianthol.
Examples of vitamins which can be added include vitamin A, such as vitamin A oil, retinol, retinyl acetate and retinyl palmitate; vitamin B, including vitamin B2 such as riboflavin, riboflavin butyrate and flavin adenine nucleotide, vitamin B6 such as pyridoxine hydrochloride, pyridoxine dioctanoate and pyridoxine tripalmitate, vitamin B12 and its derivatives, and vitamin B15 and its derivatives; vitamin C, such as L-ascorbic acid, L-ascorbic acid dipalmitic ester, sodium (L-ascorbic acid) -2-sulfate and dipotassium L-ascorbic acid diphosphate; vitamin D, such as ergocalciferol and cholecarciferol; vitamin E, such as xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, dl-xcex1-tocopheryl acetate, dl-xcex1-tocopheryl nicotinate and dl-xcex1-tocopheryl succinate; vitamin H; vitamin P; nicotinic acids, such as nicotinic acid, benzyl nicotinate and nicotinic acid amide; pantothenic acids, such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether and acetylpantothenyl ethyl ether; and biotin.
Examples of an amino acid which can be added include glycine, valine, leucine, isoleucine, serine, threonine, phenylaranine, alginine, lysine, aspartic acid, aspartic acid, glutamic acid, cystine, cysteine, methionine, and tryptophan; those of a nucleic acid which can be added include deoxyribonucleic acid; and those of hormone which can be added include estradiol and ethenyl estradiol.
The term xe2x80x9ccosmetic materialxe2x80x9d as used herein are intended to include skin care products, such as face lotion, milky lotion, cream, face cleansing cream, massage materials, toilet soap and detergent, antiperspirant and deodorant; makeup products, such as face powder, foundation, rouge, eye shadow, mascara, eyeliner and lipstick; and hairdressing products, such as shampoo, rinse and treatment. Additionally, the present cosmetic material may have any of forms, including liquid, emulsion, solid, paste, gel and spray forms, if desired.
The present invention will now be illustrated in greater detail by reference to the following examples and comparative examples. However, the invention should not be construed as being limited to these examples. And the term xe2x80x9c%xe2x80x9d used hereinafter means xe2x80x9c% by weightxe2x80x9d unless noted otherwise.
Additionally, the entire disclosure of all applications, patents and publications, cited above and below, and of corresponding Japanese applications No. 11-186201, filed on Jun. 30, 1999, and 2000-169265, filed on Jun. 21, 2000, is hereby incorporated by reference.